Classifications

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  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
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  • C07C251/32—Oximes
  • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
  • C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
  • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
  • A01N41/10—Sulfones; Sulfoxides
• • A—HUMAN NECESSITIES
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  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
  • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
  • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
  • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
  • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
  • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
  • C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
  • C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
  • C07C45/46—Friedel-Crafts reactions
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D333/28—Halogen atoms
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

• the present invention relates to 2-benzoylcyclohexane-1,3-diones of the formula I
• R 1 , R 2 are hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, —OR 5 , —OCOR 6 , —OSO 2 R 6 , —SH, —S(O) n R 7 , —SO 2 OR 5 , —SO 2 NR 5 R 8 , —NR 8 SO 2 R 6 or —NR 8 COR 6 ;
• R 3 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 4 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, —COR 9 , —CO 2 R 9 , —COSR 9 or —CONR 8 R 9 , it being possible for the abovementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals and for R 9 of the radicals —COR 9 , —CO 2 R 9 , —COSR 9 and —CONR 8 R 9 to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
• X is oxygen or sulfur
• Z is oxygen or NR 8 ;
• n 0 or 1
• n 0, 1 or 2;
• R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 6 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl
• R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 8 is hydrogen or C 1 -C 6 -alkyl
• R 9 is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, phenyl or benzyl;
• R 10 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• Q is an unsubstituted or substituted cyclohexane-1,3-dione ring which is linked in the 2-position;
• the invention relates to processes and to intermediates for the preparation of compounds of the formula I, to compositions comprising them, and to the use of the compounds of the formula I and of compositions comprising them for controlling harmful plants.
• compositions which comprise the compounds I and which have a very good herbicidal activity.
• processes for the preparation of these compositions and methods of controlling undesired vegetation using the compounds I are also known.
• the compounds of the formula I can also contain one or more chiral centers, in which case they are present as enantiomer or diastereomer mixtures.
• the invention relates to the pure enantiomers or diastereomers and also to mixtures of these.
• the compounds of the formula I can also exist in the form of their agriculturally useful salts, the type of salt generally being unimportant.
• suitable salts are salts of those cations or the acid addition salts of those acids whose cations, or anions, respectively, do not adversely affect the herbicidal activity of the compounds I.
• Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, it being possible in this case, if desired, for one to four hydrogen atoms to be replaced by C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl and/or a phenyl or benzyl, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, in addition phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(C 1 -C 4 -alkyl)sulfoxonium.
• Anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
• R 11 , R 12 , R 14 and R 16 are hydrogen or C 1 -C 4 -alkyl
• R 13 is hydrogen, C 1 -C 4 -alkyl or C 3 -C 4 -cycloalkyl, it being possible for the two last-mentioned groups to have attached to them one to three of the following substituents:
• tetrahydropyran-2-yl is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,4-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, it being possible for the 6 last-mentioned radicals to be substituted by one to three C 1 -C 4 -alkyl radicals;
• R 15 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 6 -alkoxycarbonyl
• R 13 and R 16 together form a ⁇ bond or a three to six-membered carbocycylic ring
• the CR 13 R 14 unit can be replaced by C ⁇ O.
• R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 4 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, —COR 9 , —CO 2 R 9 , —COSR 9 or —CONR 8 R 9 , it being possible for the abovementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals and for R 9 of the radicals —COR 9 , —CO 2 R 9 , —COSR 9 and —CONR 8 R 9 to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
• the organic moieties mentioned for the substituents R 1 -R 16 or as radicals on phenyl, hetaryl and heterocyclyl rings are collective terms for individual enumerations of the individual group members.
• All hydrocarbon chains ie. all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkoxyamino, alkylthio, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyl, cycloalkenyl, alkynyl moieties can be straight-chain or branched.
• halogenated substituents preferably have attached to them one to five identical or different halogen atoms. Halogen is in each case fluorine, chlorine, bromine or iodine.
• C 2 -C 4 -alkyl ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
• C 1 -C 6 -alkyl and the alkyl moieties of C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl: C 2 -C 6 -alkyl as mentioned above, and also methyl;
• C 1 -C 4 -haloalkyl a C 1 -C 4 -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl
• C 1 -C 6 -haloalkyl C 1 -C 4 -haloalkyl as mentioned above, and also 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;
• C 1 -C 6 -alkoxy and the alkoxy moieties of C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy-C 2 -C 6 -alkoxycarbonyl and C 1 -C 6 -alkoxycarbonyl: C 1 -C 4 -alkoxy as mentioned above, and also pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy [sic], 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethy
• C 1 -C 4 -haloalkoxy a C 1 -C 4 -alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-
• C 1 -C 4 -alkylthio methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;
• C 1 -C 4 -alkylsulfonyl (C 1 -C 4 -alkyl-S( ⁇ O) 2 -): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;
• C 1 -C 4 -alkyliminooxy methyliminooxy, ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy, 1-butyliminooxy and 2-butyliminooxy;
• C 3 -C 6 -alkenyl prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en
• C 2 -C 6 -alkenyl C 3 -C 6 -alkenyl as mentioned above, and also ethenyl;
• C 3 -C 6 -alkynyl prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4
• C 2 -C 6 -alkynyl C 3 -C 6 -alkynyl as mentioned above, and also ethynyl;
• C 3 -C 4 -cycloalkyl cyclopropyl and cyclobutyl
• C 3 -C 6 -cycloalkyl C 3 -C 4 -cycloalkyl as mentioned above, and also cyclopentyl and cyclohexyl;
• C 4 -C 6 -cycloalkenyl cyclobuten-1-yl, cyclobuten-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclopenten-4-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;
• heterocyclyl and the heterocyclyl radicals in heterocyclyloxy: three to seven-membered saturated or partially unsaturated mono- or polycyclic heterocycles which contain one to three hetero atoms selected from a group consisting of oxygen, nitrogen and sulfur, such as oxiranyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidin
• hetaryl and the hetaryl radicals in hetaryloxy: aromatic mono- or polycyclic radicals which, besides carbon ring members, additionally can contain one to four nitrogen atoms or one to three nitrogen atoms and an oxygen or a sulfur atom or an oxygen or a sulfur atom, eg.
• All phenyl and hetaryl rings are preferably unsubstituted or have attached to them one to three halogen atoms and/or one or two radicals selected from the group which follows: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy and methoxycarbonyl.
• the variables preferably have the following meanings, in each case alone or in combination:
• R 1 is nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, —OR 5 or —S(O) n R 7 ;
• nitro, halogen eg. fluorine, chlorine or bromine, C 1 -C 6 -haloalkyl, eg. trifluoromethyl, —OR 5 or —SO 2 R 7 ;
• R 2 is hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, —OR 5 or —S(O) n R 7 ;
• R 3 is hydrogen, C 1 -C 6 -alkyl, eg. methyl, ethyl, propyl or butyl, or C 1 -C 6 -haloalkyl, eg. difluoromethyl or trifluoromethyl;
• R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, it being possible for the 4 last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups: hydroxyl, mercapto, amino, cyano, —OR 10 , ⁇ NOR 10 , —OCOR 10 , —CO 2 R 10 , —COSR 10 , —CONR 8 R 10 , C 1 -C 4 -alkyliminooxy, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-C 2 -C 6 -alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, phenyl-C 1 -C 4 -alkyl, hetaryl, phen
• X is oxygen or sulfur
• Z is oxygen, NH or NCH 3 ;
• n 0 or 1
• n 0 or 2
• R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 8 is hydrogen or C 1 -C 6 -alkyl
• R 10 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 11 , R 12 , R 14 , R 16 are hydrogen or C 1 -C 4 -alkyl
• R 13 is hydrogen, C 1 -C 4 -alkyl, C 3 -C 4 -cycloalkyl, it being possible for the two last-mentioned groups to be unsubstituted or to have attached to them one to three of the following substituents: halogen, C 1 -C 4 -alkoxy or C 1 -C 4 -alkylthio;
• R 15 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxycarbonyl
• R 13 and R 16 may be advantageous for R 13 and R 16 to form a ⁇ bond so that a double bond system results.
• the CR 13 R 14 unit can be replaced advantageously by C ⁇ O.
• R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, it being possible for the 4 last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups: hydroxyl, mercapto, amino, cyano, —OR 10 , ⁇ NOR 10 , —OCOR 10 , —CO 2 R 10 , —COSR 10 , —CONR 8 R 10 , C 1 -C 4 -alkyliminooxy, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-C 2 -C 6 -alkoxycarbonyl, heterocyclyl, heterocyclyloxy, phenyl, phenyl-C 1 -C 4 -alkyl, hetaryl, phen
• the compounds Ia4 especially the compounds Ia4.1-Ia4.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 15 and R 16 are in each case methyl:
• the compounds Ia7 especially the compounds Ia7.1-Ia7.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 11 , R 12 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia9 especially the compounds Ia9.1-Ia9.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is nitro and R 13 is methyl:
• the compounds Ia10 especially the compounds Ia10.1-Ia10.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is nitro and R 13 and R 14 are in each case methyl:
• the compounds Ia11 especially the compounds Ia11.1-Ia11.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is nitro and R 15 and R 16 are in each case methyl:
• the compounds Ia12 especially the compounds Ia12.1-Ia12.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is nitro and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia13 especially the compounds Ia13.1-Ia13.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is nitro, R 11 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia14 especially the compounds Ia14.1-Ia14.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is nitro, R 11 , R 12 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia15 especially the compounds Ia15.1-Ia15.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl:
• the compounds Ia16 especially the compounds Ia16.1-Ia16.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl and R 13 is methyl:
• the compounds Ia17 especially the compounds Ia17.1-Ia17.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl and R 13 and R 14 are in each case methyl:
• the compounds Ia18 especially the compounds Ia18.1-Ia18.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl and R 15 and R 16 are in each case methyl:
• the compounds Ia19 especially the compounds Ia19.1-Ia19.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia20 especially the compounds Ia20.1-Ia20.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl, R 11 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia21 especially the compounds Ia21.1-Ia21.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is methylsulfonyl, R 11 , R 12 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia23 especially the compounds Ia23.1-Ia23.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is trifluoromethyl and R 13 is methyl:
• the compounds Ia24 especially the compounds Ia24.1-Ia24.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is trifluoromethyl and R 13 and R 14 are in each case methyl:
• the compounds Ia25 especially the compounds Ia25.1-Ia25.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is trifluoromethyl and R 15 and R 16 are in each case methyl:
• the compounds Ia26 especially the compounds Ia26.1-Ia26.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is trifluoromethyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia27 especially the compounds Ia27.1-Ia27.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is trifluoromethyl, R 11 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• the compounds Ia28 especially the compounds Ia28.1-Ia28.2790, which differ from the corresponding compounds Ia1.1-Ia1.2790 by the fact that R 1 is trifluoromethyl, R 11 , R 12 , R 15 and R 16 are in each case methyl and the CR 13 R 14 unit is replaced by C ⁇ O:
• R 1 is halogen or C 1 -C 4 -alkylsulfonyl
• R 2 is halogen or C 1 -C 4 -alkyl
• R 3 is hydrogen or C 1 -C 4 -alkyl
• R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, it being possible for the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups: phenyl, phenyl-C 1 -C 4 -alkyl, hetaryl or phenyloxy, it being possible for the 4 last-mentioned radicals in turn to be partially or fully halogenated;
• X is oxygen
• Z is oxygen or NH
• n 0 or 1
• R 12 R 12 , R 14 , R 15 , R 16 are hydrogen or C 1 -C 4 -alkyl
• R 13 is hydrogen, C 1 -C 4 -alkyl, tetrahydropyran-3-yl, tetrahydrothiopyran-3-yl or 1,4-dioxan-2-yl;
• the CR 13 R 14 unit can be replaced by C ⁇ O.
• the 2-benzoylcyclohexane-1,3-diones of the formula I are obtainable by various routes, for example by the following process:
• L 1 is a nucleophilically displaceable leaving group such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate and the like.
• halogen eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate and the like.
• the activated carboxylic acid can be employed directly, as in the case of the carboxylic acid halides, or generated in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfite/triphenylphosphine, carbonyldiimidazole and the like.
• auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
• the reactants and the auxiliary base are expediently employed in equimolar amounts for this purpose.
• a small excess mount of the auxiliary base for example 1.2 to 1.5 mol equivalents based on II, may be advantageous under certain circumstances.
• Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates.
• solvents which can be used are chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide or esters such as ethyl acetate, or mixtures of these.
• carboxylic acid halides are employed as activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10° C. when adding this reactant.
• the mixture is subsequently stirred at 20-100° C., preferably at 25-500° C., until the reaction is complete.
• Working-up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of value is extracted.
• Solvents which are especially suitable for this purpose are methylene chloride, diethyl ether and ethyl acetate.
• the crude enol ester of the formula IV is purified, preferably by chromatography. However, it is also possible to employ the crude enol ester of the formula IV in the rearrangement reaction without further purification.
• the enol esters of the formula IV are expediently subjected to a rearrangement reaction to give the compounds of the formula I at from 20 to 40° C. in a solvent and in the presence of an auxiliary base and with the aid of, or without, a cyano compound as catalyst.
• Solvents which can be used are, for example, acetonitrile, ethylene chloride, 1,2-dichloroethane, ethyl acetate, toluene, or mixtures of these.
• the preferred solvent is acetonitrile.
• Suitable auxiliary bases are tertiary amines such as triethylamine, pyridine or alkali metal carbonates such as sodium carbonate, potassium carbonate, which are preferably employed in quimolar amounts or up to a fourfold excess, based on the enol ester.
• triethylamine is used, preferably in twice the equimolar ratio based on the enol ester.
• Suitable as “rearrangement catalysts” are inorganic cyanides such as sodium cyanide, potassium cyanide, and organic cyano compounds such as acetone cyanohydrin, trimethylsilyl cyanide. They are normally employed in an amount of from 1 to 50 mol percent, based on the enol ester. It is preferred to employ acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent based on the enol ester.
• the reaction mixture is acidified with dilute mineral acid, eg. 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, eg. methylene chloride, ethyl acetate.
• the organic extract can be extracted with 5-10% strength alkali metal carbonate solution, eg. sodium carbonate solution, potassium carbonate solution.
• the aqueous phase is acidified and the resulting precipitate filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated.
• Those cyclohexane-1,3-diones of the formula II which are used as starting materials and which are not already known can be prepared by processes known per se (for example EP-A 71 707, EP-A 142 741, EP-A 243 313, U.S. Pat. No. 4 249 937; WO 92/13821).
• R 1 , R 2 are hydrogen, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, —OR 5 , —OCOR 6 , —OSO 2 R 6 , —SH, —S(O) n R 7 , —SO 2 OR 5 , —SO 2 NR 5 R 8 , —NR 8 SO 2 R 6 or —NR 8 COR 6 ;
• R 3 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 4 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, —COR 9 , —CO 2 R 9 , —COSR 9 or —CONR 8 R 9 , it being possible for the abovementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl radicals and for R 9 of the radicals —COR 9 , —CO 2 R 9 , —COSR 9 and —CONR 8 R 9 to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
• X is oxygen or sulfur
• Z is oxygen or NR 8 ;
• n 0 or 1
• n 0, 1 or 2;
• R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 6 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl
• R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 4 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 8 is hydrogen or C 1 -C 6 -alkyl
• R 9 is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, phenyl or benzyl;
• R 10 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl;
• R 17 is hydroxyl or a radical which can be removed by hydrolysis
• radicals which can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals which are unsubstituted or substituted, halides, hetaryl radicals which are bonded via nitrogen, amino radicals, imino radicals which are unsubstituted or substituted.
• L 1 is halogen, in particular chlorine or bromine.
• M is C 1 -C 6 -alkoxy
• halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride, oxalyl bromide
• Isophthalic acid derivatives of the formula VI can be obtained in a manner known per se by oxidizing aldehydes of the formula V (J. March, “Advanced Organic Chemistry”, 3rd Edition (1985), p. 629 et seq., Wiley-Interscience Publication).
• aldehydes of the formula V can be synthesized from the corresponding toluenes of the formula VIII by processes similar to those known from the literature by converting them into the ⁇ -halotoluene IX and subsequently oxidizing the product (cf. Synth. Commun. 22 (1992), 1967-1971).
• the carboxylic acids of the formula VI are accessible by hydrolyzing nitriles of the formula X by processes known from the literature (J. March, “Advanced Organic Chemistry”, 3rd Edition (1970), p. 788, Wiley-Interscience Publication, 1985; Ann. Chem. (1970), p. 23-37).
• nitrites of the formula X can be synthesized from the corresponding aldehydes V by processes similar to those known from the literature (J. March, “Advanced Organic Chemistry”, 3rd Edition (1985), pp. 806-807, Wiley-Interscience Publication). Equally, it is possible to obtain nitrites of the formula X from anilines of the formula XI by means of Sandmeyer reaction or from aryl halides of the formula XII by Rosemund/von Braun reaction with metal cyanides, in particular CUCN (J. March, “Advanced Organic Chemistry”, 1985, 3rd Edition, p. 594, p. 648, Wiley-Interscience Publication).
• Step c) 2-Chloro-3-methyl-4-methylsulfonylbenzoic acid 82 g (0.33 mol) of 2-chloro-3-methyl-4-methylsulfonyl-acetophenone were dissolved in 700 ml of dioxane, and 1 l of a 12.5% strength sodium hypochlorite solution was added at room temperature. Stirring was subsequently continued for 1 hour at 800° C. After cooling, two phases formed, of which the bottom phase was diluted with water and acidified weakly. The solid which precipitated was filtered off with suction, washed with water and dried. This gave 60 g (73% of theory) of 2-chloro-3-methyl-4-methylsulfonylbenzoic acid.
• the 2-benzoylcyclohexane-1,3-diones of the formula I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers.
• the herbicidal compositions comprising compounds of the formula I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, soybeans and cotton they act against broad-leaved weeds and grass weeds without damaging the crop plants substantially. This effect is observed especially at low rates of application.
• the compounds of the formula I, or compositions comprising them can additionally be employed in a further number of crop plants for eliminating undesirable plants.
• suitable crops are the following:
• the compounds of the formula I can also be used in crops which tolerate the action of herbicides due to breeding including genetic engineering methods.
• the compounds of the formula I or the herbicidal compositions comprising them can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
• directly sprayable aqueous solutions, powders, suspensions also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
• the use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
• the herbicidal compositions comprise a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I and auxiliaries conventionally used for the formulation of crop protection products.
• Suitable inert additives are essentially: mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone, and strongly polar solvents, e.g. amines such as N-methylpyrrolidone and water.
• mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffin, tetrahydronaphthalene, alkylated na
• Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
• the substrates substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier.
• Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylaryl sulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxyethylene oct
• Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
• Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
• Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
• the concentrations of the compounds of the formula I in the ready-to-use products can be varied within wide ranges.
• the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
• the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
• the compounds I according to the invention can be formulated, for example, as follows:
• V. 3 parts by weight of the active ingredient No. 2.09 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active ingredient.
• the active ingredients of the formula I, or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact, if any, with the leaves of the sensitive crop plants while the active ingredients reach the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).
• the compounds of the formula I can be mixed and applied jointly with a large number of representatives of other groups of herbicidally or growth-regulatory active ingredients.
• Suitable components in mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (het)aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ethers, diazines, dichloropropionic acid and its derivatives, dihydrobenzo
• the rates of application of active ingredient are from 0.001 to is 3.0, preferably 0.01 to 1.0, kg/ha active substance (a.s.), depending on the purpose of the control measures, the season, the target plants and the growth stage.
• the culture containers used were plastic pots containing loamy sand with approximately 3.0% of humus as substrate.
• the seeds of the test plants were sown separately for each species.
• the active ingredients suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles.
• the containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants unless this was adversely affected by the active ingredients.
• test plants were first grown to a plant height of from 3 to 15 cm, depending on the plant habit, and then treated with the active ingredients which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.
• the rate of application for the post-emergence treatment was 0.125 or 0.0625 kg/ha a.s.
• the plants were kept at from 10-25° C. and 20-35° C., respectively.
• the test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
• Evaluation was carried out using a scale of from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth.

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